Titanium dioxide, TiO₂, materials have received much attention in recent years due to their potential use as intercalation negative electrodes for rechargeable lithium-ion batteries. The aim of this doctoral work was to synthesise and characterise new titanium dioxide nanomaterials and to investigate their electrochemical behaviour. Three morphologies of TiO₂(B) phase: micro-sized (bulk), nanowires and nanotubes, were synthesised. All three exhibit properties which make them excellent hosts for lithium intercalation. The nanotubes show the best capability of accommodating lithium in the structure, being able to host over one molar equivalent of lithium at low current rates (5 mA g⁻¹). The lithium insertion mechanism in the TiO₂(B) was studied using powder neutron diffraction. In addition, the nature of the irreversible capacity of the nanotubes was studied and ways of reducing it proposed. Nanotubes of another titanium dioxide polymorph, anatase, were synthesised and characterised. Their electrochemical performance was compared with that of commercially available counterparts with different morphologies and particle sizes. The interrelation between particle size/morphology and electrochemical properties has been established. The insertion of lithium which leads to phase variations was studied using in situ Raman microscopy and neutron powder diffraction. It has been demonstrated that doping of the TiO₂(B) nanotubes with vanadium improves their electronic conductivity which is essential for practical applications. Remarkably good electrochemical performance is exhibited by the 6% V-doped TiO₂(B) nanotubes.

abstract: There is a fundamental attractiveness about harnessing renewable energy in an age when sustainability is an ethical norm. Lithium ion batteries and hydrogen fuels are considered the most promising energy source instead of fossil fuels. This work describes the investigation of new cathode materials and devices architectures for lithium ion batteries, and photocatalysts for their usage in water splitting and waste water treatment. LiCoO2 and LiNi1/3Mn1/3Co1/3O2 were exfoliated into nanosheets using electrochemical oxidation followed by intercalation of tetraethylammonium cations. The nanosheets were purified using dialysis and electrophoresis. The nanosheets were successfully restacked into functional cathode materials with microwave hydrothermal assistance, indicating that new cathodes can be obtained by reassembling nanosheets. This method can pave the way for the synthesis of materials with novel structures and electrochemical properties, as well as facilitate the fabrication of hybrid and composite structures from different nanosheets as building blocks. Paper folding techniques are used in order to compact a Li-ion battery and increase its energy per footprint area. Full cells were prepared using Li4Ti5O12 and LiCoO2 powders deposited onto current collectors consisting of paper coated with carbon nanotubes. Folded cells showed higher areal capacities compared to the planar versions. Origami lithium-ion battery made in this method that can be deformed at an unprecedented high level, including folding, bending and twisting. Spray pyrolysis was used to prepare films of AgInS2 with and without Sn as an extrinsic dopant. The photoelectrochemical performance of these films was evaluated after annealing under a N2 or S atmosphere with different amounts of the Sn dopant. Density Function Theory (DFT) was used to calculate the band structure of AgInS2 and understand the role of Sn doping in the observed properties. Cr(VI) removal was investigated using multiple oxide photocatalyst and additives. The efficiency for Cr(VI) removal using these photocatalysts was investigated in synthetic neutral and alkaline water, as well as in cooling tower blowdown water. While sulfite alone can chemically reduce Cr(VI), sulfite in combination with a photocatalyst resulted in faster and complete removal of Cr(VI) in 10 min using a SO32−/Cr(VI) ratio >35 in pH ∼ 8 solutions. / Dissertation/Thesis / Doctoral Dissertation Materials Science and Engineering 2016

abstract: Lithium ion batteries prepared with a ceramic separator, have proven to possess improved safety, reliability as well as performance characteristics when compared to those with polymer separators which are prone to thermal runaway. Purely inorganic separators are highly brittle and expensive. The electrode-supported ceramic separator permits thinner separators which are a lot more flexible in comparison. In this work, it was observed that not any α-alumina could be used by the blade coating process to get a good quality separator on Li4Ti5O12 (LTO) electrode. In this work specifically, the effect of particle size of α-alumina, on processability of slurry was investigated. The effect of the particle size variations on quality of separator formation was also studied. Most importantly, the effect of alumina particle size and its distribution on the performance of LTO/Li half cells is examined in detail. Large-sized particles were found to severely limit the ability to fabricate such separators. The α-alumina slurry was coated onto electrode substrate, leading to possible interaction between α-alumina and LTO substrate. The interaction between submicron sized particles of α-alumina with the substrate electrode pores, was found to affect the performance and the stability of the separator. Utilizing a bimodal distribution of submicron sized particles with micron sized particles of α-alumina to prepare the separator, improved cell performance was observed. Yet only a specific ratio of bimodal distribution achieved good results both in terms of separator formation and resulting cell performance. The interaction of α-alumina and binder in the separator, and its effect on the performance of substrate electrode was investigated, to understand the need for bimodal distribution of powder forming the separator. / Dissertation/Thesis / Masters Thesis Chemical Engineering 2017

Ces travaux ont permis d'approfondir les mécanismes de (dé)lithiation et de vieillissement dans des électrodes à base de silicium et de LiFePO4 pour accumulateurs Li-ion à partir d'observations multi-échelles. Des cartographies de phases, autant à l'échelle de la particule qu'à l'échelle de l'électrode, ont été menées par microscopie électronique mettant en évidence de fortes hétérogénéités. Pour le silicium, la mise en place de cartographie unique par STEM/EELS, s'appuyant sur une base de données des pertes faibles d'alliages sensibles à l'air et au faisceau d'électrons, a permis de comprendre les mécanismes de lithiation à l'échelle du nanomètre. L'étude de la première lithiation a montré des différences de mécanismes de réaction avec le lithium suivant deux facteurs : la taille des particules et les défauts au sein de celles-ci. Il a été observé une composition d'alliage LixSi plus faible pour les nanoparticules que pour les microparticules. Les défauts dus notamment au broyage constituent des sites préférentiels de lithiation. En vieillissement, les nanoparticules subissent de profonds changements structuraux et morphologiques, passant d'un état sphérique cristallin (50 nm) à un réseau de fils amorphe (5-10 nm d'épaisseur) contenu dans une matrice de SEI. Pour le LiFePO4, il a été clairement montré, par la combinaison de plusieurs techniques de microscopies électroniques (diffraction des électrons en précession, EFSD : Electron Forward Scattering Diffraction, EFTEM), que les particules de taille nanométrique (100-200 nm) étaient soit entièrement lithiées soit entièrement délithiées à l'équilibre thermodynamique. De fortes hétérogénéités ont été observées dans les électrodes fines comme dans les électrodes épaisses. A l'échelle des particules, l'analyse statistique de plus de 64000 particules a montré que les plus petites particules se délithient en premier. A l'échelle de l'agglomérat, les cartographies de phases ont révélé un mécanisme « cœur-coquille » : la réaction débute de la surface vers le centre des agglomérats. A l'échelle de l'électrode, le front de propagation de phase se déplace suivant des chemins préférentiels de plus grandes porosités de la surface de l'électrode vers le collecteur de courant. La conductivité ionique au sein de nos électrodes est le facteur limitant. / This work aimed at better understanding the (de)lithiation and aging mechanisms in LiFePO4 and silicon-based electrodes for Li-ion batteries from multiscale investigations. Phase mapping was performed by electron microscopy at the particle scale and at the electrode scale. This highlights some strong heterogeneities. The silicon study has shown some different lithium reaction mechanisms following two effects: particle size and crystalline defects. A smaller lithium amount in LixSi alloy was highlighted for the nanoparticles rather than for the microparticles. The defects mainly due to milling are preferential sites for the lithiation. In aging, the nanoparticles have undergone structural and morphological changes. The pristine crystalline spherical shape (50 nm) was transformed into an amorphous wire network (5-10 nm of thickness) contained in a SEI matrix. Thanks to a combination of electron microscopy techniques (precession electron diffraction, Electron Forward Scattering Diffraction, EFTEM), it was clearly shown that the LiFePO4 particles (100-200 nm) are either fully lithiated or fully delithiated at the thermodynamic equilibrium. Strong heterogeneities were observed in the thin and thick electrodes. At the nanoscale, the statistical analysis of 64000 particles unambiguously shows that the small particles delithiate in first. At the mesoscale, the phase maps reveal a core-shell mechanism at the scale of the agglomerates, from the surface to the center of these agglomerates. At the electrode scale, the phase front would move following preferential paths into the higher porosity from the surface in contact with electrolyte toward the current collector. The electrode ionic conductivity is the limiting parameter.

Submitted by Lucienne Costa (lucienneferreira@ufcg.edu.br) on 2018-05-11T22:51:17Z No. of bitstreams: 1 JOSÉ ETIMÓGENES DUARTE SEGUNDO – TESE (PPGEQ) 2017.pdf: 3042948 bytes, checksum: e0c377da642dbbf1ba0a1022f463d9de (MD5) / Made available in DSpace on 2018-05-11T22:51:17Z (GMT). No. of bitstreams: 1 JOSÉ ETIMÓGENES DUARTE SEGUNDO – TESE (PPGEQ) 2017.pdf: 3042948 bytes, checksum: e0c377da642dbbf1ba0a1022f463d9de (MD5) Previous issue date: 2018-08-31 / Para satisfazer aplicações industriais e o crescente consumo de combustíveis fósseis, têm-se realizado várias pesquisas sobre o desenvolvimento de materiais e tecnologias para o armazenamento de energia de forma sustentável e renovável. O grafeno é um material que despertou interesse de estudos recentes devido às suas excelentes propriedades físico-químicas, mecânicas, térmicas, elétricas e ópticas. Em uma bateria de íons de lítio, o grafeno supera as limitações de capacidade do grafite, comumente usado como material anódico. Neste trabalho, estudou-se o uso de monocamada de grafeno como ânodo em uma bateria de íons de lítio para verificar a influência da densidade de corrente e da composição do eletrólito no desempenho eletroquímico do material. A densidade de corrente foi aplicada em três níveis diferentes: 3, 5 e 10 μA/cm2. O eletrólito testado foi LiPF6 1M em etilenocarbonato/dietilcarbonato (50/50v) (EC-DEC), etilmetilcarbonato (EMC) ou propilenocarbonato (PC). As análises de microscopia de força atômica e Raman exibiram uma monocamada de grafeno uniforme sobre a superfície do substrato. Os espectros de impedância eletroquímica da célula descarregada foram analisados para investigar a cinética do processo de eletrodo nos diferentes eletrólitos. Os resultados mostraram um processo controlado pela transferência de carga, mas com grande contribuição da difusão de íons de lítio. Na caracterização eletroquímica, os melhores resultados foram obtidos para o eletrólito EC-DEC. A capacidade irreversível no 1º ciclo variou de 11,39 a 77,47%, em função da densidade de corrente aplicada, e maior capacidade de descarga foi de 21 575 mAh/g, para 3 μA/cm2. Com a aplicação dessa mesma densidade de corrente, a eficiência coulômbica média foi de 67,12% e a capacidade de descarga sofreu redução de 87,90%, ao longo de 20 ciclos. Os resultados obtidos confirmaram o grande potencial do grafeno para aplicação em sistemas de armazenamento de energia. / To satisfy industrial applications and the growing consumption of fossil fuels, researches have been performed on the development of materials and technologies for energy storage in a renewable and sustainable way. Graphene is a material that has interested recent studies due to its excellent physical-chemical, mechanical, thermal, electrical and optical properties. In a lithium-ion battery, graphene overcomes the capacity limitations of graphite, commonly used as anode material. In this work, monolayer graphene using as anode was studied in a lithium-ion battery to verify the influence of current density and electrolyte composition on the electrochemical performance of electrode material. Current density was applied in three different levels: 3, 5 and 10 μA/cm2. The electrolyte tested was LiPF6 1M in ethylene carbonate/diethyl carbonate (50/50v) (EC-DEC), ethyl methyl carbonate (EMC) or propylene carbonate (PC). AFM and Raman microscopy analysis exhibited a uniform monolayer graphene over substrate surface. The EIS spectra of discharged cell were analyzed to investigate the kinetics of electrode process in different electrolytes. Results showed a process controlled by charge transfer but with great contribution of lithium-ion diffusion in case of EC-DEC solvent. Irreversible capacity in the 1st cycle ranged from 11.39 to 77.47%, as function of applied current density, and the highest discharge capacity was 21,575 mAh/g, for 3 μA/cm2. With application of this current density value, the average coulombic efficiency was 67.12% and the discharge capacity was reduced by 87.90% over 20 cycles. Results confirmed the great potential of graphene for application in energy storage systems.

abstract: Novel materials for Li-ion batteries is one of the principle thrust areas for current research in energy storage, more so than most, considering its widespread use in portable electronic gadgets and plug-in electric and hybrid cars. One of the major limiting factors in a Li-ion battery's energy density is the low specific capacities of the active materials in the electrodes. In the search for high-performance anode materials for Li-ion batteries, many alternatives to carbonaceous materials have been studied. Both cubic and amorphous silicon can reversibly alloy with lithium and have a theoretical capacity of 3500 mAh/g, making silicon a potential high density anode material. However, a large volume expansion of 300% occurs due to changes in the structure during lithium insertion, often leading to pulverization of the silicon. To this end, a class of silicon based cage compounds called clathrates are studied for electrochemical reactivity with lithium. Silicon-clathrates consist of silicon covalently bonded in cage structures comprised of face sharing Si20, Si24 and/or Si28 clusters with guest ions occupying the interstitial positions in the polyhedra. Prior to this, silicon clathrates have been studied primarily for their superconducting and thermoelectric properties. In this work, the synthesis and electrochemical characterization of two categories of silicon clathrates - Type-I silicon clathrate with aluminum framework substitution and barium guest ions (Ba8AlxSi46-x) and Type-II silicon clathrate with sodium guest ions (Nax Si136), are explored. The Type-I clathrate, Ba8AlxSi46-x consists of an open framework of aluminium and silicon, with barium (guest) atoms occupying the interstitial positions. X-ray diffraction studies have shown that a crystalline phase of clathrate is obtained from synthesis, which is powdered to a fine particle size to be used as the anode material in a Li-ion battery. Electrochemical measurements of these type of clathrates have shown that capacities comparable to graphite can be obtained for up to 10 cycles and lower capacities can be obtained for up to 20 cycles. Unlike bulk silicon, the clathrate structure does not undergo excessive volume change upon lithium intercalation, and therefore, the crystal structure is morphologically stable over many cycles. X-ray diffraction of the clathrate after cycling showed that crystallinity is intact, indicating that the clathrate does not collapse during reversible intercalation with lithium ions. Electrochemical potential spectroscopy obtained from the cycling data showed that there is an absence of formation of lithium-silicide, which is the product of lithium alloying with diamond cubic silicon. Type II silicon clathrate, NaxSi136, consists of silicon making up the framework structure and sodium (guest) atoms occupying the interstitial spaces. These clathrates showed very high capacities during their first intercalation cycle, in the range of 3,500 mAh/g, but then deteriorated during subsequent cycles. X-ray diffraction after one cycle showed the absence of clathrate phase and the presence of lithium-silicide, indicating the disintegration of clathrate structure. This could explain the silicon-like cycling behavior of Type II clathrates. / Dissertation/Thesis / M.S. Materials Science and Engineering 2013

abstract: In engineering, buckling is mechanical instability of walls or columns under compression and usually is a problem that engineers try to prevent. In everyday life buckles (wrinkles) on different substrates are ubiquitous -- from human skin to a rotten apple they are a commonly observed phenomenon. It seems that buckles with macroscopic wavelengths are not technologically useful; over the past decade or so, however, thanks to the widespread availability of soft polymers and silicone materials micro-buckles with wavelengths in submicron to micron scale have received increasing attention because it is useful for generating well-ordered periodic microstructures spontaneously without conventional lithographic techniques. This thesis investigates the buckling behavior of thin stiff films on soft polymeric substrates and explores a variety of applications, ranging from optical gratings, optical masks, energy harvest to energy storage. A laser scanning technique is proposed to detect micro-strain induced by thermomechanical loads and a periodic buckling microstructure is employed as a diffraction grating with broad wavelength tunability, which is spontaneously generated from a metallic thin film on polymer substrates. A mechanical strategy is also presented for quantitatively buckling nanoribbons of piezoelectric material on polymer substrates involving the combined use of lithographically patterning surface adhesion sites and transfer printing technique. The precisely engineered buckling configurations provide a route to energy harvesters with extremely high levels of stretchability. This stiff-thin-film/polymer hybrid structure is further employed into electrochemical field to circumvent the electrochemically-driven stress issue in silicon-anode-based lithium ion batteries. It shows that the initial flat silicon-nanoribbon-anode on a polymer substrate tends to buckle to mitigate the lithiation-induced stress so as to avoid the pulverization of silicon anode. Spontaneously generated submicron buckles of film/polymer are also used as an optical mask to produce submicron periodic patterns with large filling ratio in contrast to generating only ~100 nm edge submicron patterns in conventional near-field soft contact photolithography. This thesis aims to deepen understanding of buckling behavior of thin films on compliant substrates and, in turn, to harness the fundamental properties of such instability for diverse applications. / Dissertation/Thesis / Ph.D. Mechanical Engineering 2014

Fundação de Amparo a Pesquisa no Estado do Rio Grande do Sul / The increasing industrial development results in a large consumption of products and materials. Among them, stand out the polymeric materials, due to their versatility and low cost, and electrical and electronic equipment (EEE), such as mobile phones and their batteries. In this scenario, an efficient and environmentally friendly recycling technology has a great importance. Therefore, this study presents an alternative to the mechanical recycling of these wastes. The separation of the polymeric mixtures was performed using the triboelectrostatic separation process. The components of lithium-ion batteries were recovered by a corona electrostatic separation process. In polymeric waste processing, the methodology employed was the characterization, washing, drying, comminution, secondary washing, secondary drying, tribocharging and electrostatic separation of the different polymeric blends (HDPE / PP, LDPE / PP and PET / PVC). The variables studied were the tribocharging mechanism, the relative humidity, the tribocharging residence time, the angle of the deflector, the distance of the static electrode, the electrode voltage and the rotation of the roll. In lithium ion batteries waste processing, the methodology employed was the characterization, comminution, drying, particle size separation and electrostatic separation. The selected parameters were the electrodes voltage, cylinder rotation, the distance of the static electrode and the angle of the deflector of the collector. For the polymeric waste processing the best results were: low relative humidity, tribocharging residence time of 5 minutes, angle of the deflector of 2.5 °, the distance of the static electrode of 3 cm, voltage of 30 kV and speed rotation 10 rpm. With these parameters, was obtained the recovery of 92.8% of PP (purity of 95.7%) and 95.9% of HDPE (purity of 93.1%). In the separation of PP and LDPE, was obtained a PP recovery of 90.2% (purity 93.8%) and a LDPE recovery of 94.2% (purity of 90.8%). Also, was achieved a recovery of 96.8% of PET (purity of 95.9%), and recovery of 95.9% for PVC (purity of 96.8%). For lithium ion batteries waste processing the best conditions were: rotation speed of 20 rpm, voltage of 25 kV, distance of the static electrode 6 cm and angle of the deflector 0 °. Through this process, was obtained a conductive fraction with 98.98% of metals content and a nonconductive fraction with 99.6% of polymer. The characterization of the batteries showed the batteries heterogeneity, being the electrostatic separation efficient to the different models tested. Therefore, the application of electrostatic separation is a promising method and efficient to recycling of polymer waste and lithium ion batteries waste. The studied process enabled a significant recovery of the components with a high purity. / O crescente desenvolvimento industrial acarreta em um grande consumo de produtos e materiais. Entre eles, destacam-se os materiais poliméricos, devido à sua versatilidade e baixo custo, e os equipamentos elétricos e eletrônicos (EEE), tais como os telefones celulares e suas baterias. Nesse cenário, tecnologias de reciclagem eficientes e ambientalmente aceitáveis tem uma grande importância. Diante disso, o presente trabalho apresenta uma alternativa para a reciclagem mecânica destes diferentes resíduos. A separação das misturas poliméricas foi realizada através do processo de separação triboeletrostática. Já os diferentes componentes das baterias de íon de lítio foram recuperados por um processo de separação eletrostática por efeito corona. No processamento dos resíduos poliméricos, a metodologia empregada consistiu na caracterização, lavagem, cominuição, lavagem e secagem secundária, tribocarregamento e separação eletrostática das diferentes misturas poliméricas (PEAD/PP, PEBD/PP e PET/PVC). As variáveis estudadas foram o mecanismo de tribocarregamento, a umidade relativa do ar, tempo de tribocarregamento, ângulo do defletor, distância do eletrodo de atração, tensão dos eletrodos e a rotação do rolo. No processamento das baterias de íon de lítio, realizaram-se a caracterização das baterias, cominuição, secagem, separação granulométrica e separação eletrostática. Os parâmetros selecionados foram a tensão dos eletrodos, rotação do rolo, distância do eletrodo de atração e o ângulo do defletor do coletor. Para o processamento dos resíduos poliméricos os melhores resultados foram: umidade relativa do ar de ± 42%, tempo de tribocarregamento de 5 minutos, ângulo do defletor de 2,5°, distância do eletrodo de atração de 3 cm, tensão de 30 kV e velocidade de rotação de 10 rpm. Com esses parâmetros, obteve-se a recuperação de 92,8% de PP (pureza de 95,7%) e 95,9% de PEAD (pureza de 93,1%). Na separação de PP e PEBD, obteve-se uma recuperação de PP de 90,2% (pureza de 93,8%), e uma recuperação de PEBD de 94,2% (pureza de 90,8%). Também, conseguiu-se uma recuperação de 96,8% de PET (pureza de 95,9%), e de 95,9% de PVC (pureza de 96,8%). Para a reciclagem de baterias de íon de lítio as melhores condições foram: velocidade de rotação de 20 rpm, tensão de 25 kV, distância do eletrodo de atração de 6 cm e ângulo do defletor de 0°. Através deste processamento, obteve-se uma fração condutora com 98,98% de metais e uma fração não condutora com 99,6% de polímeros. A caracterização das baterias demonstrou uma heterogeneidade desse tipo de resíduo, sendo o processo de separação eletrostática eficiente para os diferentes modelos testados. Sendo assim, a aplicação da separação eletrostática se mostrou um método eficiente e promissor para a reciclagem de resíduos poliméricos e de resíduos de baterias de íon de lítio. O processo estudado possibilitou a obtenção de uma expressiva recuperação dos componentes com uma alta pureza.

Dans les accumulateurs au lithium, l'électrolyte joue un rôle important car ses propriétés physicochimiques et électrochimiques conditionnent l'efficacité du générateur électrochimique. Actuellement, les électrolytes organiques utilisés induisent des difficultés pour la mise en oeuvre et l'utilisation de la batterie (composants volatils et inflammables). De nouveaux électrolytes à base de sels fondus à température ambiante, dit liquides ioniques, sont des candidats potentiels plus sécuritaires (faible inflammabilité, basse pression de vapeur saturante, point éclair élevé), qui présentent en outre une large fenêtre électrochimique. Dans un premier temps, le travail de thèse a été de concevoir de nouvelles voies de synthèses plus économes, tenant compte des exigences environnementales (limitation des déchets, pas de solvant) et proposant des liquides ioniques de haute pureté >99.5% compatibles avec une production industrielle. De nouveaux liquides ioniques dérivés du cation imidazolium ont alors été conçus afin de moduler leurs propriétés physicochimiques et optimiser leurs performances dans les batteries. Ils ont été évalués dans diverses technologies de batteries (Graphite/LiFePO4) et (Li4Ti5O12/LiFePO4) dans différentes conditions expérimentales, à 298 K et 333 K, cette dernière température étant proscrite pour les batteries conventionnelles. Ce travail de thèse a permis d'identifier les modifications chimiques pour conduire aux électrolytes les plus prometteurs et à mis en exergue l'importance de l'étude de la compréhension des phénomènes d'interphase liquides ioniques/ électrodes / In lithium ion batteries, the electrolyte plays an important role because its physicochemical and electrochemical properties determine their efficiency. Currently, the used organic electrolytes induce difficulties in the manufacturing and the use of the battery (volatile and flammable components). New electrolytes based on molten salts at room temperature, called ionic liquids, are safer potential candidates (low flammability, low vapor pressure, high flash point) with a wide electrochemical window. The first stage of this PhD was to design new and more efficient synthetic routes, taking into account the environmental requirements (waste minimization, no solvent) and allowing the elaboration of ionic liquids with high purity> 99.5%, compatible with an industrial production. New ionic liquids derived from imidazolium cation were then designed in order to modulate their physicochemical properties, and to optimize their performance in batteries. They were evaluated in various battery technologies (Graphite/LiFePO4) and (Li4Ti5O12/LiFePO4) under different experimental conditions, 298 K and 333 K, when the conventional lithium ion batteries (organic electrolyte) are used only under 313 K. This PhD work has identified the chemical modifications to yield the most promising electrolytes, and highlighted the importance of the study on the understanding of ionic liquid/electrode interphase phenomena

Ce mémoire est consacré à l'étude théorique des matériaux de cathode pour batteries Li-ion de structure olivine LiMPO4 (M=Mn, Fe, Co, Ni), des phases délithiées MPO4 et des phases mixtes LiFexMn1-xPO4, FexMn1-xPO4 et LiFexCo1-xPO4. La stabilité des phases magnétiques et les paramètres de maille théoriques ont été déterminés par la méthode des pseudopotentiels et comparés aux données expérimentales. Les structures électroniques ont été calculées par une méthode « tout électron » et analysées en termes d'hybridation des orbitales atomiques Ces résultats ont permis d'interpréter les spectres de photoélectrons X et d'absorption des rayons X, en particulier les modifications réversibles associées aux cycles de lithiation/délithiation. Les effets de la polarisation de spin et de la corrélation électronique ont été discutés. Enfin, le calcul des paramètres Mössbauer du 57Fe a montré qu'un accord quantitatif entre les résultats théoriques et les données expérimentales nécessitait la prise en compte de ces deux effets. Ce type de calcul a permis de prédire et d'expliquer que la transformation LiFePO4FePO4 s'accompagnait de la variation du gradient de champ électrique Vzz d'une extrémité à l'autre de l'échelle Mössbauer pour 57Fe. / This thesis is devoted to the theoretical study of the cathode materials for Li-ion batteries with olivine structure LiMPO4 (M=Mn, Fe, Co, Ni), the delithiated phases MPO4 and the mixed phases LiFexMn1-xPO4, FexMn1-xPO4 and LiFexCo1-xPO4. The magnetic phase stability and lattice parameters were theoretically determined from pseudopotential calculations and the results have been compared with experiments. Electronic structures were obtained from all electron calculations and analyzed in terms of orbital hybridization. The results have been used for the interpretation of X-ray photoemission and X-ray absorption spectra, especially changes due to lithiation/delithiation cycles. Effects of spin polarization and electronic correlation on the electronic structures have been also discussed. It has been shown that ab initio calculations of the 57Fe Mössbauer parameters also require these two effects in order to obtain a quantitative agreement with experiments. Finally, it was found that LiFePO4FePO4 transformation involves a dramatic change of the electric field gradient VZZ from one end to the other of the 57Fe Mössbauer scale.